Aryl-condensed 3-arylpridine compounds and use thereof for controlling pathogenic fungi

ABSTRACT

The present invention relates to bicyclic compounds of general formula I,  
                 
in which 
     X, Y independently of one another are N or C—R 4 ; n is 1, 2, 3, 4 or 5;    R a  is halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkyl, C 1 -C 6 -haloalkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkenyloxy or C(O)R 5 ;    R 1  is halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -cycloalkyl which is optionally mono- or polysubstituted by alkyl and/or halogen, C 5 -C 8 -cycloalkenyl which is optionally mono- or polysubstituted by alkyl and/or halogen, OR 6 , SR 6  or NR 7 R 8 ;    R 2  is halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 8 -cycloalkyl which is optionally mono- or polysubstituted by alkyl and/or halogen, C 5 -C 8 -cycloalkenyl which is optionally mono- or polysubstituted by alkyl and/or halogen, OR 6 , SR 6  or NR 7 R 8 ;    R 3  is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or C 3 -C 6 -cycloalkyl which is optionally mono- or polysubstituted by alkyl and/or halogen; and the agriculturally acceptable salts of compounds I, plant protection agents, containing at least one compound of general formula I and/or one agriculturally-acceptable salt of I and at least one liquid or solid carrier substance, as well as a method for controlling phytopathogenic fungi.

The present invention relates to novel aryl-fused 3-arylpyridinecompounds and to their use for controlling harmful fungi, and also tocrop protection compositions comprising such compounds as activecomponent.

EP-A 71792, U.S. Pat. No. 5,994,360, EP-A 550113 and WO 02/48151describe fungicidally active pyrazolo[1,5-a]pyrimidines andtriazolo[1,5a]pyrimidines which carry an optionally substituted phenylgroup in the 5-position of the pyrimidine ring.Imidazolo[1,2-a]pyrimidines having fungicidal action are known from WO03/022850.

In principle, there is a constant demand for novel fungicidally activecompounds to widen the activity spectrum and to prevent a possibledevelopment of resistance against known fungicides. Novel activecompounds should kill the harmful fungi at application rates which areas low as possible and reduce or, even better, prevent theirre-establishment. Moreover, the active compounds should be welltolerated by useful plants, i.e. they should cause little, if any,damage to the useful plants.

U.S. Pat. No. 5,801,183 and WO 96/22990 describe2,4-dihydroxy-1,8-naphthyridines which carry an optionally substitutedphenyl radical in the 3-position, as aza analogs of glycine/NMDAreceptor antagonists.

The compounds 4-hydroxy-3-(o-methoxyphenyl)-1,8-naphthyridin-2-(1H)-oneand 2,4-dichloro-3-(o-methoxyphenyl)-1,8-naphthyridine are known from J.of Heterocyclic Chemistry, 30, 1993, 909-912, and4-hydroxy-3-(4-methoxyphenyl)-1,8-naphthyridin-2-(1H)-one,4-hydroxy-3-(4-methylphenyl)-1,8-naphthyridin-2-(1H)-one,4-hydroxy-3-(3-methylphenyl)-1,8-naphthyridin-2-(1H)-one and4-hydroxy-3-(2-methylphenyl)-1,8-naphthyridin-2-(1H)-one are known fromChem. Ber. 111, 2813-2824 (1978).

With a view to a possible development of resistance and to widening ofthe activity spectrum, it is of fundamental interest to provide novelactive compounds.

Accordingly, it is an object of the present invention to provide novelcompounds having good fungicidal activity, in particular at lowapplication rates, and/or good compatibility with useful plants. Thisobject is achieved by bicyclic, i.e. aryl-fused, 3-arylpyridinecompounds of the formula I

in which

-   X, Y independently of one another are N or C—R⁴;-   n is 1, 2, 3, 4 or 5;-   R^(a) is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl,    C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy or C(O)R⁵;-   R¹ is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl,    C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono- or    polysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which is    optionally mono- or polysubstituted by alkyl and/or halogen, OR⁶,    SR⁶ or NR⁷R⁸;-   R² is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl,    C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono- or    polysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which is    optionally mono- or polysubstituted by alkyl and/or halogen, OR⁶,    SR⁶ or NR⁷R⁸;-   R³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl or C₃-C₆-cycloalkyl    which is optionally mono- or polysubstituted by alkyl and/or    halogen;-   R⁴ is hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl or    C₃-C₆-cycloalkyl which is optionally mono- or polysubstituted by    alkyl and/or halogen;-   R⁵ is hydrogen, OH, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl,    C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₁-C₆-alkylamino or    di-C₁-C₆-alkylamino, piperidin-1-yl, pyrrolidin-1-yl or    morpholin-4-yl;-   R⁶ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, phenyl-C₁-C₄-alkyl    where phenyl may be mono- or polysubstituted by halogen, alkyl or    alkoxy, C₂-C₆-alkenyl or COR⁹;-   R⁷, R⁸ independently of one another are hydrogen, C₁-C₁₀-alkyl,    C₂-C₁₀-alkenyl, C₄-C₁₀-alkadienyl, C₂-C₁₀-alkynyl, C₃-C₈-cycloalkyl,    C₅-C₈-cycloalkenyl, C₅-C₁₀-bicycloalkyl, phenyl, phenyl-C₁-C₄-alkyl,    naphthyl,    -   a 5- or 6-membered saturated or partially unsaturated        heterocycle which may have 1, 2 or 3 heteroatoms selected from        the group consisting of N, O and S as ring members, or    -   a 5- or 6-membered aromatic heterocycle which may have 1, 2 or 3        heteroatoms selected from the group consisting of N, O and S as        ring members,    -   where the radicals mentioned as R⁷, R⁸ may be partially or fully        halogenated and/or may have 1, 2 or 3 radicals R^(b), where        -   R^(b) is selected from the group consisting of cyano, nitro,            OH, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl,            C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₂-C₆-alkenyl,            C₂-C₆-alkenyloxy, C₂-C₆-alkynyl, C₂-C₆-alkynyloxy,            C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, piperidin-1-yl,            pyrrolidin-1-yl or morpholin-4-yl;-   R⁷ and R⁸ together with the nitrogen atom to which they are attached    may also form a 5-, 6- or 7-membered saturated or unsaturated    heterocycle which may have 1, 2, 3 or 4 further heteroatoms selected    from the group consisting of O, S, N and NR¹⁰ as ring members and    may be partially or fully halogenated and which may have 1, 2 or 3    radicals R^(b); and-   R⁹, R¹⁰ independently of one another are hydrogen or C₁-C₆-alkyl;    and the agriculturally acceptable salts of compounds I.

Accordingly, the present invention provides the use of the bicycliccompounds of the formula I and their agriculturally acceptable salts forcontrolling phytopathogenic fungi (=harmful fungi), and a method forcontrolling phytopathogenic harmful fungi which comprises treating thefungi or the materials, plants, the soil or seed to be protected againstfungal attack with an effective amount of the compound of the formula Iand/or with an agriculturally acceptable salt of I.

Except for the 1,8-naphthyridines mentioned in U.S. Pat. No. 5,801,183,in WO 96/22990, in J. of Heterocyclic Chemistry, 30, 1993, 909-912 andin Chem. Ber. 111, 2813-2824 (1978), the compounds I are novel.Accordingly, the present invention also relates to bicyclic compounds ofthe formula I and agriculturally acceptable salts thereof, except for:

compounds of the formula I in which R¹ is OH if Y and X aresimultaneously each C—R⁴; and also

-   -   2,4-dichloro-3-(o-methoxyphenyl)-1,8-naphthyridine.

The present invention furthermore provides a composition for controllingharmful fungi, comprising at least one compound of the formula I and/oran agriculturally acceptable salt thereof and at least one liquid orsolid carrier.

Depending on the substitution pattern, the compounds of the formula Imay have one or more centers of chirality, in which case they arepresent as pure enantiomers or diastereomers or as mixtures ofenantiomers or diastereomers. The invention provides both the pureenantiomers or diastereomers and their mixtures. The invention alsoprovides tautomers of compounds of the formula I.

Suitable agriculturally useful salts are especially the salts of thosecations or the acid addition salts of those acids whose cations andanions, respectively, have no negative effect on the fungicidal actionof the compounds I. Thus, suitable cations are in particular the ions ofthe alkali metals, preferably sodium and potassium, of the alkalineearth metals, preferably calcium, magnesium and barium, and of thetransition metals, preferably manganese, copper, zinc and iron, and alsothe ammonium ion which, if desired, may carry one to four C₁-C₄-alkylsubstituents and/or one phenyl or benzyl substituent, preferablydiisopropylammonium, tetramethylammonium, tetrabutylammonium,trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions,preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferablytri(C₁-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide,fluoride, hydrogensulfate, sulfate, dihydrogenphosphate,hydrogenphosphate, phosphate, nitrate, hydrogencarbonate, carbonate,hexafluorosilicate, hexafluorophosphate, benzoate, and the anions ofC₁-C₄-alkanoic acids, preferably formate, acetate, propionate andbutyrate. They can be formed by reacting I with an acid of thecorresponding anion, preferably hydrochloric acid, hydrobromic acid,sulfuric acid, phosphoric acid or nitric acid.

In the definitions of the variables given in the formulae above,collective terms are used which are generally representative for therespective substituents. The term C_(n)-C_(m) denotes the number ofcarbon atoms possible in each case in the respective substituent orsubstituent moiety:

halogen: fluorine, chlorine, bromine and iodine;

-   alkyl and all alkyl moieties in alkoxy, alkylthio, alkylamino and    dialkylamino: saturated straight-chain or branched hydrocarbon    radicals having 1 to 4, to 6, to 8 or to 10 carbon atoms, for    example C₁-C₆-alkyl, such as methyl, ethyl, propyl, 1-methylethyl,    butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl,    1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,    1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,    1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,    1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,    2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,    1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,    1,2,2-trimethylproyl, 1-ethyl-1-methylpropyl and    1-ethyl-2-methylpropyl;    haloalkyl: straight-chain or branched alkyl groups having 1 to 4 or    to 6 carbon atoms (as mentioned above), where some or all of the    hydrogen atoms in these groups may be replaced by halogen atoms as    mentioned above, for example C₁-C₂-haloalkyl, such as chloromethyl,    bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,    difluoromethyl, trifluoromethyl, chlorofluoromethyl,    dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,    1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,    2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,    2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,    2,2,2-trichloroethyl, pentafluoroethyl and 1,1,1-trifluoroprop-2-yl;    phenyl-C₁-C₄-alkyl: a C₁-C₄-alkyl group as mentioned above which is    substituted by phenyl, for example benzyl, 1-phenylethyl,    2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl,    3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl,    3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl,    2-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl,    1-(phenylmeth)eth-1-yl, 1-(phenylmethyl)-1-(methyl)eth-1-yl or    -(phenylmethyl)-1-(methyl)prop-1-yl; preferably benzyl;    phenyl-C₁-C₄-alkyl which is optionally mono- or polysubstituted by    halogen, alkoxy or alkyl: a phenyl-substituted C₁-C₄-alkyl group,    where the phenyl group unsubstituted or may carry 1, 2, 3 or 4,    preferably 1, substituent(s) selected from the group consisting of    fluorine, chlorine, bromine, C₁-C₆-alkoxy and C₁-C₆-alkyl, for    example p-bromophenylmethyl, p-chlorophenylmethyl,    p-methylphenylmethyl, p-methylphenylmethyl, p-methoxyphenylmethyl,    p-methoxyphenylethyl;    alkenyl: monounsaturated straight-chain or branched hydrocarbon    radicals having 2 to 4, to 6, to 8 or to 10 carbon atoms and a    double bond in any position, for example C₂-C₆-alkenyl, such as    ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl,    2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl,    1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,    3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,    3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,    3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,    3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,    1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,    1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,    3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,    2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,    1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,    4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,    3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,    2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,    1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,    1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,    1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,    1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,    2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,    2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,    3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,    1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,    2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,    1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and    1-ethyl-2-methyl-2-propenyl;    alkadienyl: diunsaturated straight-chain or branched hydrocarbon    radicals having 4 to 10 carbon atoms and two double bonds in any    position, for example 1,3-butadienyl, 1-methyl-1,3-butadienyl,    2-methyl-1,3-butadienyl, penta-1,3-dien-1-yl, hexa-1,4-dien-1-yl,    hexa-1,4-dien-3-yl, hexa-1,4-dien-6-yl, hexa-1,5-dien-1-yl,    hexa-1,5-dien-3-yl, hexa-1,5-dien-4-yl, hepta-1,4-dien-1-yl,    hepta-1,4-dien-3-yl, hepta-1,4-dien-6-yl, hepta-1,4-dien-7-yl,    hepta-1,5-dien-1-yl, hepta-1,5-dien-3-yl, hepta-1,5-dien-4-yl,    hepta-1,5-dien-7-yl, hepta-1,6-dien-1-yl, hepta-1,6-dien-3-yl,    hepta-1,6-dien-4-yl, hepta-1,6-dien-5-yl, hepta-1,6-dien-2-yl,    octa-1,4-dien-1-yl, octa-1,4-dien-2-yl, octa-1,4-dien-3-yl,    octa-1,4-dien-6-yl, octa-1,4-dien-7-yl, octa-1,5-dien-1-yl,    octa-1,5-dien-3-yl, octa-1,5-dien-4-yl, octa-1,5-dien-7-yl,    octa-1,6-dien-1-yl, octa-1,6-dien-3-yl, octa-1,6-dien-4-yl,    octa-1,6-dien-5-yl, octa-1,6-dien-2-yl, deca-1,4-dienyl,    deca-1,5-dienyl, deca-1,6-dienyl, deca-1,7-dienyl, deca-1,8-dienyl,    deca-2,5-dienyl, deca-2,6-dienyl, deca-2,7-dienyl, deca-2,8-dienyl    and the like;    alkynyl: straight-chain or branched hydrocarbon groups having 2 to    4, 2 to 6, 2 to 8 or 2 to 10 carbon atoms and a triple bond in any    position, for example C₂-C₆-alkynyl, such as ethynyl, 1-propynyl,    2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl,    1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-ethyl-2-butynyl,    1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,    1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,    3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,    1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,    2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,    4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,    1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,    2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,    1-ethyl-3-butynyl, 2-ethyl-3-butynyl and    1-ethyl-1-methyl-2-propynyl;    cycloalkyl: monocyclic saturated hydrocarbon groups having 3 to 8,    preferably to 6, carbon ring members, such as cyclopropyl,    cyclobutyl, cyclopentyl and cyclohexyl;    cycloalkyl which is optionally mono- or polysubstituted by halogen    or alkyl: a cycloalkyl group as mentioned above which is    unsubstituted or carries 1, 2, 3 or 4, preferably 1, substituent(s),    where the substituent(s) is/are selected from the group consisting    of fluorine, chlorine, bromine and C₁-C₆-alkyl, for example    4-chlorocyclohexyl, 4-bromocyclohexyl, 4-methoxycyclohexyl,    4-ethylcyclohexyl, 2-chlorocyclopropyl, 2-fluorocyclopropyl,    1-chlorocyclopropyl, 1-fluorocyclopropyl;    cycloalkenyl: monocyclic monounsaturated hydrocarbon groups having 5    to 8, preferably 6, carbon ring members, such as cyclopenten-1-yl,    cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and    cyclohexen-4-yl;    cycloalkenyl which is optionally mono- or polysubstituted by halogen    or alkyl: a cycloalkenyl group as mentioned above which is    unsubstituted or carries 1, 2, 3 or 4, preferably 1, substituent(s),    where the substituent(s) is/are selected from the group consisting    of fluorine, chlorine, bromine and C₁-C₆-alkyl, for example    4-chlorocyclohexen-1-yl, 4-bromocyclohexen-1-yl,    4-methylcyclohexen-1-yl, 4-ethylcyclohexen-1-yl,    4-chlorocyclohexen-3-yl, 4-bromocyclohexen-3-yl,    4-methylcyclohexen-3-yl, 4-ethylcyclohexen-3-yl;    bicycloalkyl: a bicyclic hydrocarbon radical having 5 to 10 carbon    atoms, such as bicyclo[2.2.1]hept-1-yl, bicyclo[2.2.1]hept-2-yl,    bicyclo[2.2.1]hept-7-yl, bicyclo[2.2.2]oct-1-yl,    bicyclo[2.2.2]oct-2-yl, bicyclo[3.3.0]octyl and bicyclo[4.4.0]decyl;    C₁-C₄-alkoxy: an alkyl group having 1 to 4 carbon atoms which is    attached via oxygen: for example methoxy, ethoxy, n-propoxy,    1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or    1,1-dimethylethoxy;    C₁-C₆-alkoxy: C₁-C₄-alkoxy as mentioned above, and also, for    example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy,    1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy,    1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy,    3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy,    1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy,    2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy,    2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy,    1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy;    C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above which is    partially or fully substituted by fluorine, chlorine, bromine and/or    iodine, preferably by fluorine, i.e., for example, OCH₂F, OCHF₂,    OCF₃, OCH₂Cl, OCHCl₂, OCCl₃, chlorofluoromethoxy,    dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy,    2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy,    2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,    2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,    2,2,2-trichloroethoxy, OC₂F₅, 2-fluoropropoxy, 3-fluoropropoxy,    2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy,    3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy,    3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,    OCH₂—C₂F₅, OCF₂—C₂F₅, 1-(CH₂F)-2-fluoroethoxy,    1-(CH₂Cl)-2-chloroethoxy, 1-(CH₂Br)-2-bromoethoxy, 4-fluorobutoxy,    4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy;    C₁-C₆-haloalkoxy: C₁-C₄-haloalkoxy as mentioned above, and also, for    example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy,    5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy,    6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;    alkenyloxy: alkenyl as mentioned above which is attached via an    oxygen atom, for example C₂-C₆-alkenyloxy, such as vinyloxy,    1-propenyloxy, 2-propenyloxy, 1-methylethenyloxy, 1-butenyloxy,    2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy,    2-methyl-1-propenyloxy, 1-methyl-2-propenyloxy,    2-methyl-2-propenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy,    4-pentenyloxy, 1-methyl-1-butenyloxy, 2-methyl-1-butenyloxy,    3-methyl-1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy,    3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy,    3-methyl-3-butenyl, 1,1-dimethyl-2-propenyloxy,    1,2-dimethyl-1-propenyloxy, 1,2-dimethyl-2-propenyloxy,    1-ethyl-1-propenyloxy, 1-ethyl-2-propenyloxy, 1-hexenyloxy,    2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy,    1-methyl-1-pentenyloxy, 2-methyl-1-pentenyloxy,    3-methyl-1-pentenyloxy, 4-methyl-1-pentenyloxy,    1-methyl-2-pentenyloxy, 2-methyl-2-pentenyloxy,    3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy,    1-methyl-3-pentenyloxy, 2-methyl-3-pentenyloxy,    3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy,    1-methyl-4-pentenyloxy, 2-methyl-4-pentenyloxy,    3-methyl-4-pentenyloxy, 4-methyl-4-pentenyloxy,    1,1-dimethyl-2-butenyloxy, 1,1-dimethyl-3-butenyloxy,    1,2-dimethyl-1-butenyloxy, 1,2-dimethyl-2-butenyloxy,    1,2-dimethyl-3-butenyloxy, 1,3-dimethyl-1-butenyloxy,    1,3-dimethyl-2-butenyloxy, 1,3-dimethyl-3-butenyloxy,    2,2-dimethyl-3-butenyloxy, 2,3-dimethyl-1-butenyloxy,    2,3-dimethyl-2-butenyloxy, 2,3-dimethyl-3-butenyloxy,    3,3-dimethyl-1-butenyloxy, 3,3-dimethyl-2-butenyloxy,    1-ethyl-1-butenyloxy, 1-ethyl-2-butenyloxy, 1-ethyl-3-butenyloxy,    2-ethyl-1-butenyloxy, 2-ethyl-2-butenyloxy, 2-ethyl-3-butenyloxy,    1,1,2-trimethyl-2-propenyloxy, 1-ethyl-1-methyl-2-propenyloxy,    1-ethyl-2-methyl-1-propenyloxy and 1-ethyl-2-methyl-2-propenyloxy;    alkynyloxy: alkynyl as mentioned above which is attached via an    oxygen atom, for example C₃-C₆-alkynyloxy, such as 2-propynyloxy,    2-butynyloxy, 3-butynyloxy, 1-methyl-2-propynyloxy, 2-pentynyloxy,    3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy,    1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-ethyl-2-propynyloxy,    2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy,    1-methyl-2-pentynyloxy, 1-methyl-3-pentynyloxy and the like;    a five- or six-membered saturated or partially unsaturated    heterocycle which comprises one, two or three heteroatoms from the    group consisting of oxygen, nitrogen and sulfur: for example mono-    and bicyclic heterocycles (heterocyclyl) which, in addition to    carbon ring members, comprise one to three nitrogen atoms and/or one    oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for    example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl,    2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl,    3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl,    5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,    5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl,    5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl,    2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl,    4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,    1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,    1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,    1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,    1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl,    2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl,    2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl,    2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl,    2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl,    2-isoxazolin-4-yl 3-isoxazolin-4-yl, 4-isoxazolin-4-yl,    2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl,    2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl,    2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl,    2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl,    2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl,    2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl,    2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl,    3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl,    3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl,    4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,    4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl,    2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl,    2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,    3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl,    3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl,    3,4-diyydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl,    3-piperidinyl, 4-piperidinyl, 1,3-dioxan-5-yl, 2-tetrahydropyranyl,    4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl,    4-hexahydropyridazinyl, 2-hexahydropyrimidinyl,    4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl,    1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl;    a five- or six-membered aromatic heterocycle which comprises one,    two or three heteroatoms from the group consisting of oxygen,    nitrogen or sulfur: mono- or bicyclic heteroaryl, for example    5-membered heteroaryl which is attached via carbon and comprises one    to three nitrogen atoms or one or two nitrogen atoms and one sulfur    or oxygen atom as ring members, such as 2-furyl, 3-furyl, 2-thienyl,    3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl,    5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl,    3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl,    5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl,    4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl,    1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl,    1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl and 1,3,4-triazol-2-yl;    5-membered heteroaryl which is attached via nitrogen and contains    one to three nitrogen atoms as ring members, such as pyrrol-1-yl,    pyrazol-1-yl, imidazol-1-yl, 1,2,3-triazol-1-yl and    1,2,4-triazol-1-yl; 6-membered heteroaryl which comprises one to    three nitrogen atoms one to three nitrogen atoms as ring members,    such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl,    4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl,    2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.

A first embodiment of the present invention relates to compounds of theformula I in which X and Y are each C—R⁴, where the radicals R⁴ may ineach case be identical or different. Hereinbelow, these compounds arereferred to as compounds I.a.

A further preferred embodiment of the present invention relates tocompounds of the formula I in which X is C—R⁴ and Y is N. Hereinbelow,these compounds are referred to as compounds I.b.

A further preferred embodiment of the present invention relates tocompounds of the formula I in which X is N and Y is C—R⁴. Hereinbelow,these compounds are referred to as compounds I.c.

In the formulae of the formula I.a, I.b and I.c, the variables R^(a), n,R¹, R², R³ and R⁴ have the meanings given above, in particular themeanings given below as being preferred.

With a view to the use of the compounds I according to the invention asfungicides, the variables n, R^(a), R¹, R², R³ and R⁴ independently ofone another and preferably in combination have the following meanings:

-   n is 2, 3, 4 or 5, in particular 2 or 3;-   R^(a) is halogen, in particular fluorine or chlorine, C₁-C₄-alkyl,    in particular methyl, C₁-C₄-alkoxy, in particular methoxy,    C₁-C₂-fluoroalkyl, in particular difluoromethyl and trifluoromethyl,    C₁-C₂-fluoroalkoxy, in particular difluoromethoxy and    trifluoromethoxy, C₁-C₄-alkoxycarbonyl, in particular    methoxycarbonyl and cyano. Particularly preferably, R^(a) is    selected from the group consisting of halogen, especially fluorine    or chlorine, C₁-C₄-alkyl, especially methyl, and C₁-C₄-alkoxy,    especially methoxy;-   R¹ is halogen, especially chlorine, hydroxyl or a group NR⁷R⁸;-   R² is halogen, especially chlorine, hydroxyl, C₁-C₆-alkyl,    especially methyl, C₁-C₆-haloalkyl or a group NR⁷R⁸;-   R³ is hydrogen, C₁-C₆-alkyl, preferably C₁-C₃-alkyl,    C₁-C₆-haloalkyl, preferably C₁-C₃-haloalkyl, and particularly    preferably hydrogen;-   R⁴ is hydrogen, halogen, C₁-C₆-alkyl, preferably C₁-C₃-alkyl,    C₁-C₆-haloalkyl, preferably C₁-C₃-haloalkyl, particularly preferably    hydrogen.

If R¹ is halogen, especially chlorine, R² is preferably halogen,especially chlorine, C₁-C₆-alkyl, especially methyl, C₁-C₆-haloalkyl ora group NR⁷R⁸.

If R¹ is hydroxyl, R² is preferably hydroxyl, C₁-C₆-alkyl orC₁-C₆-haloalkyl.

If R¹ is a group NR⁷R⁸, R² is preferably selected from halogen,especially chlorine, C₁-C₆-alkyl, especially methyl, andC₁-C₆-haloalkyl.

If R¹ is a group NR⁷R⁸, preferably at least one of the radicals R⁷, R⁸is different from hydrogen. In particular, R⁷ is C₁-C₆-alkyl,C₃-C₈-cycloalkyl which is optionally mono- or polysubstituted by alkyl,is C₁-C₆-haloalkyl, phenyl-C₁-C₄-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl.R⁸ is in particular hydrogen, C₁-C₆-alkyl or C₂-C₆-alkenyl and veryparticularly preferably hydrogen or C₁-C₄-alkyl.

The preferred groups NR⁷R⁸ include those which are a saturated orpartially unsaturated heterocyclic radical which, in addition to thenitrogen atom, may have a further heteroatom selected from the groupconsisting of O, S and NR¹⁰ as ring member and which may have one or twosubstituents selected from the group consisting of halogen, hydroxyl,C₁-C₆-alkyl and C₁-C₆-haloalkyl. Preferably, the heterocyclic radicalhas 5 to 7 atoms as ring members. Examples of such heterocyclic radicalsare pyrrolidine, piperidine, morpholine, tetrahydropyridine, for example1,2,3,6-tetrahydropyridine, piperazine and azepane, which may besubstituted in the manner mentioned above.

If R² is a group NR⁷R⁸, preferably at least one of the radicals R⁷, R⁸is different from hydrogen. In particular, R⁷ has the meanings mentionedabove as being preferred.

Preferred meanings of R^(a) include halogen, especially F or Cl,trifluoromethyl, CN, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, in particularmethoxycarbonyl.

With a view to the use of the compounds I according to the invention asfungicides,the radical

is preferably a radical of the formula

in which R^(a1) has the meanings mentioned above for R^(a) and theradicals R^(a2), R^(a3), R^(a4) and R^(a5) have the meanings given forR^(a) or are hydrogen. In particular:

-   R^(a1) is fluorine, chlorine, trifluoromethyl or methyl;-   R^(a2) is hydrogen or fluorine;-   R^(a3) is hydrogen, fluorine, chlorine, cyano, C₁-C₄-alkyl,    especially methyl, C₁-C₄-alkoxy, especially methoxy, or    C₁-C₄-alkoxycarbonyl, especially methoxycarbonyl;-   R^(a4) is hydrogen, chlorine or fluorine;-   R^(a5) is hydrogen, fluorine, chlorine or C₁-C₄-alkyl, especially    methyl, or C₁-C₄-alkoxy, especially methoxy.

Here, preferably at least one of the radicals R^(a3) or R^(a5) isdifferent from hydrogen. Preferably, at least one and particularlypreferably both radicals R^(a2), R^(a4) are hydrogen.

A preferred embodiment of the compounds I.b according to the inventionis that in which R² is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono-or polysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which isoptionally mono- or polysubstituted by alkyl and/or halogen or NR⁷R⁸ inwhich R⁷ and R⁸ are each different from hydrogen.

Another preferred embodiment of the compounds I.a and I.c according tothe invention relates to those in which R² is halogen, cyano,C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,C₃-C₈-cycloalkyl which is optionally mono- or polysubstituted by alkyland/or halogen, C₅-C₈-cycloalkenyl which is optionally mono- orpolysubstituted by alkyl and/or halogen, OR⁵, SR⁶ or N R⁷R⁸ where R⁶, R⁷and R⁸ have the meanings mentioned above and in particular the preferredmeanings.

Otherwise, the variables R³, R⁴, R⁵ and R⁶ independently of one anotherand preferably in combination with the preferred meanings of thevariables, n, R^(a), R¹ and R² have the following meanings:

-   R³ is hydrogen, C₁-C₆-alkyl, preferably C₁-C₃-alkyl,    C₁-C₆-haloalkyl, preferably C₁-C₃-haloalkyl, and particularly    preferably hydrogen;-   R⁴ is hydrogen, C₁-C₆-alkyl, preferably C₁-C₃-alkyl,    C₁-C₆-haloalkyl, preferably C₁-C₃-haloalkyl, and particularly    preferably hydrogen;-   R⁵ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy;-   R⁶ is hydrogen, C₁-C₄-alkyl, benzyl or C₁-C₄-alkylcarbonyl.

With a view to the use as fungicides, particularly preferred compoundsof the formula I are the compounds of the formulae I.a, I.b and I.c inwhich R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine or methyland (R^(a))_(n) is 2-methyl-4-chloro (compounds I.a.1, I.b.1 and I.c.1).Examples of these are compounds I.a.1, I.b.1 and I.c.1 in which R² andR¹ are each hydroxyl. Other examples are compounds I.a.1, I.b.1 andI.c.1 in which R² and R¹ are each chlorine. Other examples are compoundsI.a.1, I.b.1 and I.c.1 in which R² is methyl and R¹ is chlorine. Otherexamples are compounds I.a.1, I.b.1 and I.c.1 in which R² is methyl andR¹ is chlorine. Other examples are compounds I.a.1, I.b.1 and I.c.1 inwhich R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in eachcase the meanings given in one row of Table A. Other examples arecompounds I.a.1, I.b.1 and I.c.1 in which R² is methyl and R¹ is NR⁷R⁸,where R⁷, R⁸ together have in each case the meanings given in one row ofTable A. TABLE A No. R⁷ R⁸ A-1 CH₃ H A-2 CH₃ CH₃ A-3 CH₂CH₃ H A-4 CH₂CH₃CH₃ A-5 CH₂CH₃ CH₂CH₃ A-6 CH₂CF₃ H A-7 CH₂CF₃ CH₃ A-8 CH₂CF₃ CH₂CH₃ A-9CH₂CCl₃ H A-10 CH₂CCl₃ CH₃ A-11 CH₂CCl₃ CH₂CH₃ A-12 CH₂CH₂CH₃ H A-13CH₂CH₂CH₃ CH₃ A-14 CH₂CH₂CH₃ CH₂CH₃ A-15 CH₂CH₂CH₃ CH₂CH₂CH₃ A-16CH(CH₃)₂ H A-17 CH(CH₃)₂ CH₃ A-18 CH(CH₃)₂ CH₂CH₃ A-19 CH₂CH₂CH₂CH₃ HA-20 CH₂CH₂CH₂CH₃ CH₃ A-21 CH₂CH₂CH₂CH₃ CH₂CH₃ A-22 CH₂CH₂CH₂CH₃CH₂CH₂CH₃ A-23 CH₂CH₂CH₂CH₃ CH₂CH₂CH₂CH₃ A-24 (±)CH(CH₃)—CH₂CH₃ H A-25(±)CH(CH₃)—CH₂CH₃ CH₃ A-26 (±)CH(CH₃)—CH₂CH₃ CH₂CH₃ A-27(S)CH(CH₃)—CH₂CH₃ H A-28 (S)CH(CH₃)—CH₂CH₃ CH₃ A-29 (S)CH(CH₃)—CH₂CH₃CH₂CH₃ A-30 (R)CH(CH₃)—CH₂CH₃ H A-31 (R)CH(CH₃)—CH₂CH₃ CH₃ A-32(R)CH(CH₃)—CH₂CH₃ CH₂CH₃ A-33 (±)CH(CH₃)—CH(CH₃)₂ H A-34(±)CH(CH₃)—CH(CH₃)₂ CH₃ A-35 (±)CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-36(S)CH(CH₃)—CH(CH₃)₂ H A-37 (S)CH(CH₃)—CH(CH₃)₂ CH₃ A-38(S)CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-39 (R)CH(CH₃)—CH(CH₃)₂ H A-40(R)CH(CH₃)—CH(CH₃)₂ CH₃ A-41 (R)CH(CH₃)—CH(CH₃)₂ CH₂CH₃ A-42(±)CH(CH₃)—C(CH₃)₃ H A-43 (±)CH(CH₃)—C(CH₃)₃ CH₃ A-44 (±)CH(CH₃)—C(CH₃)₃CH₂CH₃ A-45 (S)CH(CH₃)—C(CH₃)₃ H A-46 (S)CH(CH₃)—C(CH₃)₃ CH₃ A-47(S)CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-48 (R)CH(CH₃)—C(CH₃)₃ H A-49(R)CH(CH₃)—C(CH₃)₃ CH₃ A-50 (R)CH(CH₃)—C(CH₃)₃ CH₂CH₃ A-51(±)CH(CH₃)—CF₃ H A-52 (±)CH(CH₃)—CF₃ CH₃ A-53 (±)CH(CH₃)—CF₃ CH₂CH₃ A-54(S)CH(CH₃)—CF₃ H A-55 (S)CH(CH₃)—CF₃ CH₃ A-56 (S)CH(CH₃)—CF₃ CH₂CH₃ A-57(R)CH(CH₃)—CF₃ H A-58 (R)CH(CH₃)—CF₃ CH₃ A-59 (R)CH(CH₃)—CF₃ CH₂CH₃ A-60(±)CH(CH₃)—CCl₃ H A-61 (±)CH(CH₃)—CCl₃ CH₃ A-62 (±)CH(CH₃)—CCl₃ CH₂CH₃A-63 (S)CH(CH₃)—CCl₃ H A-64 (S)CH(CH₃)—CCl₃ CH₃ A-65 (S)CH(CH₃)—CCl₃CH₂CH₃ A-66 (R)CH(CH₃)—CCl₃ H A-67 (R)CH(CH₃)—CCl₃ CH₃ A-68(R)CH(CH₃)—CCl₃ CH₂CH₃ A-69 CH₂CF₂CF₃ H A-70 CH₂CF₂CF₃ CH₃ A-71CH₂CF₂CF₃ CH₂CH₃ A-72 CH₂(CF₂)₂CF₃ H A-73 CH₂(CF₂)₂CF₃ CH₃ A-74CH₂(CF₂)₂CF₃ CH₂CH₃ A-75 CH₂C(CH₃)═CH₂ H A-76 CH₂C(CH₃)═CH₂ CH₃ A-77CH₂C(CH₃)═CH₂ CH₂CH₃ A-78 CH₂CH═CH₂ H A-79 CH₂CH═CH₂ CH₃ A-80 CH₂CH═CH₂CH₂CH₃ A-81 CH(CH₃)CH═CH₂ H A-82 CH(CH₃)CH═CH₂ CH₃ A-83 CH(CH₃)CH═CH₂CH₂CH₃ A-84 CH(CH₃)C(CH₃)═CH₂ H A-85 CH(CH₃)C(CH₃)═CH₂ CH₃ A-86CH(CH₃)C(CH₃)═CH₂ CH₂CH₃ A-87 CH₂C≡CH H A-88 CH₂C≡CH CH₃ A-89 CH₂C≡CHCH₂CH₃ A-90 cyclopentyl H A-91 cyclopentyl CH₃ A-92 cyclopentyl CH₂CH₃A-93 cyclohexyl H A-94 cyclohexyl CH₃ A-95 cyclohexyl CH₂CH₃ A-96CH₂—C₆H₅ H A-97 CH₂—C₆H₅ CH₃ A-98 CH₂—C₆H₅ CH₂CH₃ A-99 —(CH₂)₂CH═CH—CH₂—A-100 —(CH₂)₂C(CH₃)═CHCH₂— A-101 —(CH₂)₂CH(CH₃)(CH₂)₂— A-102—(CH₂)₃CHFCH₂— A-103 —(CH₂)₂CHF(CH₂)₂— A-104 —(CH₂)₂CHF(CH₂)₃— A-105—(CH₂)₂CH(CF₃)(CH₂)₂— A-106 —(CH₂)₂O(CH₂)₂— A-107 —(CH₂)₂S(CH₂)₂— A-108—(CH₂)₅— A-109 —(CH₂)₄— A-110 —CH₂CH═CHCH₂— A-111 —CH(CH₃)(CH₂)₃— A-112—CH₂CH(CH₃)(CH₂)₂— A-113 —CH(CH₃)—(CH₂)₂—CH(CH₃)— A-114 —CH(CH₃)—(CH₂)₄—A-115 —CH₂—CH(CH₃)—(CH₂)₃— A-116 —(CH₂)—CH(CH₃)—CH₂—CH(CH₃)—CH₂— A-117—CH(CH₂CH₃)—(CH₂)₄— A-118 —(CH₂)₂—CHOH—(CH₂)₂— A-119—(CH₂)—CH═CH—(CH₂)₂— A-120 —(CH₂)₆— A-121 —CH(CH₃)—(CH₂)₅— A-122—(CH₂)₂—N(CH₃)—(CH₂)₂— A-123 —N═CH—CH═CH— A-124 —N═C(CH₃)—CH═C(CH₃)—A-125 —N═C(CF₃)—CH═C(CF₃)—

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-fluoro-4-methyl (compounds I.a.2, I.b.2 andI.c.2). Examples of these are the compounds I.a.2, I.b.2 and I.c.2 inwhich R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.2, I.b.2 and I.c.2 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.2, I.b.2 and I.c.2 in which R² is methyland R¹ is chlorine. Other examples are the compounds I.a.2, I.b.2 andI.c.2 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ togetherhave in each case the meanings given in one row of Table A. Otherexamples are the compounds I.a.2, I.b.2 and I.c.2 in which R² is methyland R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case the meaningsgiven in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,6-dimethyl (compounds I.a.3, I.b.3 andI.c.3). Examples of these are the compounds I.a.3, I.b.3 and I.c.3 inwhich R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.3, I.b.3 and I.c.3 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.3, I.b.3 and I.c.3 in which R² is methyland R¹ is chlorine. Other examples are the compounds I.a.3, I.b.3 andI.c.3 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ togetherhave in each case the meanings given in one row of Table A. Otherexamples are the compounds I.a.3, I.b.3 and I.c.3 in which R² is methyland R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case the meaningsgiven in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,4,6-trimethyl (compounds I.a.4, I.b.4 andI.c.4). Examples of these are the compounds I.a.4, I.b.4 and I.c.4 inwhich R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.4, I.b.4 and I.c.4 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.4, I.b.4 and I.c.4 in which R² is methyland R¹ is chlorine. Other examples are the compounds I.a.4, I.b.4 andI.c.4 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ togetherhave in each case the meanings given in one row of Table A. Otherexamples are the compounds I.a.4, I.b.4 and I.c.4 in which R² is methyland R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case the meaningsgiven in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,6-difluoro-4-methyl (compounds I.a.5, I.b.5and I.c.5). Examples of these are the compounds I.a.5, I.b.5 and I.c.5in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.5, I.b.5 and I.c.5 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.5, I.b.5 and I.c.5 in which R² is methyland R¹ is chlorine. Other examples are the compounds I.a.5, I.b.5 andI.c.5 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ togetherhave in each case the meanings given in one row of Table A. Otherexamples are the compounds I.a.5, I.b.5 and I.c.5 in which R² is methyland R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case the meaningsgiven in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,6-difluoro-4-cyano (compounds I.a.6, I.b.6and I.c.6). Examples of these are the compounds I.a.6, I.b.6 and I.c.6in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.6, I.b.6 and I.c.6 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.6, I.b.6 and I.c.6 in which R² is methyland R¹ is chlorine. Other examples are the compounds I.a.6, I.b.6 andI.c.6 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ togetherhave in each case the meanings given in one row of Table A. Otherexamples are the compounds I.a.6, I.b.6 and I.c.6 in which R² is methyland R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case the meaningsgiven in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,6-difluoro-4-methoxycarbonyl (compoundsI.a.7, I.b.7 and I.c.7). Examples of these are the compounds I.a.7,I.b.7 and I.c.7 in which R² and R¹ are each hydroxyl. Other examples arethe compounds I.a.7, I.b.7 and I.c.7 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.7, I.b.7 and I.c.7 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.7, I.b.7 and I.c.7 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.7, I.b.7 and I.c.7 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-trifluoromethyl-4-fluoro (compounds I.a.8,I.b.8 and I.c.8). Examples of these are the compounds I.a.8, I.b.8 andI.c.8 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.8, I.b.8 and I.c.8 in which R² and R¹ are each chlorine.Other examples are the compounds I.a.8, I.b.8 and I.c.8 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.8, I.b.8and I.c.8 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ togetherhave in each case the meanings given in one row of Table A. Otherexamples are the compounds I.a.8, I.b.8 and I.c.8 in which R² is methyland R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case the meaningsgiven in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-trifluoromethyl-5-fluoro (compounds I.a.9,I.b.9 and I.c.9). Examples of these are the compounds I.a.9, I.b.9 andI.c.9 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.9, I.b.9 and I.c.9 in which R² and R¹ are each chlorine.Other examples are the compounds I.a.9, I.b.9 and I.c.9 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.9, I.b.9and I.c.9 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸ togetherhave in each case the meanings given in one row of Table A. Otherexamples are the compounds I.a.9, I.b.9 and I.c.9 in which R² is methyland R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case the meaningsgiven in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-trifluoromethyl-5-chloro (compounds I.a.10,I.b.10 and I.c.10). Examples of these are the compounds I.a.10, I.b.10and I.c.10 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.10, I.b.10 and I.c.10 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.10, I.b.10 and I.c.10 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.10, I.b.10 and I.c.10 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.10, I.b.10 and I.c.10 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-chloro-6-fluoro (compounds I.a.11, I.b.11and I.c.11). Examples of these are the compounds I.a.11, I.b.11 andI.c.11 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.11, I.b.11 and I.c.11 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.11, I.b.11 and I.c.11 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.11, I.b.11 and I.c.11 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.11, I.b.11 and I.c.11 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,6-difluoro (compounds I.a.12, I.b.12 andI.c.12). Examples of these are the compounds I.a.12, I.b.12 and I.c.12in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.12, I.b.12 and I.c.12 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.12, I.b.12 and I.c.12 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.12,I.b.12 and I.c.12 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.12, I.b.12 and I.c.12 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,6-dichloro (compounds I.a.13, I.b.13 andI.c.13). Examples of these are the compounds I.a.13, I.b.13 and I.c.13in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.13, I.b.13 and I.c.13 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.13, I.b.13 and I.c.13 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.13,I.b.13 and I.c.13 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.13, I.b.13 and I.c.13 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-fluoro-6-methyl (compounds I.a.14, I.b.14and I.c.14). Examples of these are the compounds I.a.14, I.b.14 andI.c.14 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.14, I.b.14 and I.c.14 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.14, I.b.14 and I.c.14 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.14, I.b.14 and I.c.14 in which R² is chlorine and R¹ is NR⁷R³, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.14, I.b.14 and I.c.14 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,4,6-trifluoro (compounds I.a.15, I.b.15 andI.c.15). Examples of these are the compounds I.a.15, I.b.15 and I.c.15in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.15, I.b.15 and I.c.15 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.15, I.b.15 and I.c.15 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.15,I.b.15 and I.c.15 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.15, I.b.15 and I.c.15 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,6-difluoro-4-methoxy (compounds I.a.16,I.b.16 and I.c.16). Examples of these are the compounds I.a.16, I.b.16and I.c.16 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.16, I.b.16 and I.c.16 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.16, I.b.16 and I.c.16 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.16, I.b.16 and I.c.16 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.16, I.b.16 and I.c.16 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,3,4,5,6-pentafluoro (compounds I.a.17,I.b.17 and I.c.17). Examples of these are the compounds I.a.17, I.b.17and I.c.17 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.17, I.b.17 and I.c.17 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.17, I.b.17 and I.c.17 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.17, I.b.17 and I.c.17 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R³ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.17, I.b.17 and I.c.17 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-methyl-4-fluoro (compounds I.a.18, I.b.18and I.c.18). Examples of these are the compounds I.a.18, I.b.18 andI.c.18 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.18, I.b.18 and I.c.18 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.18, I.b.18 and I.c.18 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.18, I.b.18 and I.c.18 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.18, I.b.18 and I.c.18 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-fluoro-6-methoxy (compounds I.a.19, I.b.19and I.c.19). Examples of these are the compounds I.a.19, I.b.19 andI.c.19 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.19, I.b.19 and I.c.19 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.19, I.b.19 and I.c.19 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.19, I.b.19 and I.c.19 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.19, I.b.19 and I.c.19 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,4-difluoro (compounds I.a.20, I.b.20 andI.c.20). Examples of these are the compounds I.a.20, I.b.20 and I.c.20in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.20, I.b.20 and I.c.20 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.20, I.b.20 and I.c.20 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.20,I.b.20 and I.c.20 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.20, I.b.20 and I.c.20 in which R²is methyl and R¹ is NR⁷R³, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-fluoro-4-chloro (compounds I.a.21, I.b.21and I.c.21). Examples of these are the compounds I.a.21, I.b.21 andI.c.21 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.21, I.b.21 and I.c.21 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.21, I.b.21 and I.c.21 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.21, I.b.21 and I.c.21 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.21, I.b.21 and I.c.21 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2-chloro-4-fluoro (compounds I.a.22, I.b.22and I.c.22). Examples of these are the compounds I.a.22, I.b.22 andI.c.22 in which R² and R¹ are each hydroxyl. Other examples are thecompounds I.a.22, I.b.22 and I.c.22 in which R² and R¹ are eachchlorine. Other examples are the compounds I.a.22, I.b.22 and I.c.22 inwhich R² is methyl and R¹ is chlorine. Other examples are the compoundsI.a.22, I.b.22 and I.c.22 in which R² is chlorine and R¹ is NR⁷R⁸, whereR⁷, R⁸ together have in each case the meanings given in one row of TableA. Other examples are the compounds I.a.22, I.b.22 and I.c.22 in whichR² is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each casethe meanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,3-difluoro (compounds I.a.23, I.b.23 andI.c.23). Examples of these are the compounds I.a.23, I.b.23 and I.c.23in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.23, I.b.23 and I.c.23 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.23, I.b.23 and I.c.23 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.23,I.b.23 and I.c.23 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.23, I.b.23 and I.c.23 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,5-difluoro (compounds I.a.24, I.b.24 andI.c.24). Examples of these are the compounds I.a.24, I.b.24 and I.c.24in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.24, I.b.24 and I.c.24 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.24, I.b.24 and I.c.24 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.24,I.b.24 and I.c.24 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.24, I.b.24 and I.c.24 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,3,4-trifluoro (compounds I.a.25, I.b.25 andI.c.25). Examples of these are the compounds I.a.25, I.b.25 and I.c.25in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.25, I.b.25 and I.c.25 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.25, I.b.25 and I.c.25 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.25,I.b.25 and I.c.25 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.25, I.b.25 and I.c.25 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

With a view to the use as fungicide, particularly preferred compounds ofthe formula I are furthermore the compounds of the formulae I.a, I.b andI.c in which R³ and R⁴ are each hydrogen, R² is hydroxyl, chlorine ormethyl and (R^(a))_(n) is 2,4-dimethyl (compounds I.a.26, I.b.26 andI.c.26). Examples of these are the compounds I.a.26, I.b.26 and I.c.26in which R² and R¹ are each hydroxyl. Other examples are the compoundsI.a.26, I.b.26 and I.c.26 in which R² and R¹ are each chlorine. Otherexamples are the compounds I.a.26, I.b.26 and I.c.26 in which R² ismethyl and R¹ is chlorine. Other examples are the compounds I.a.26,I.b.26 and I.c.26 in which R² is chlorine and R¹ is NR⁷R⁸, where R⁷, R⁸together have in each case the meanings given in one row of Table A.Other examples are the compounds I.a.26, I.b.26 and I.c.26 in which R²is methyl and R¹ is NR⁷R⁸, where R⁷, R⁸ together have in each case themeanings given in one row of Table A.

The compounds of the formula I according to the invention can beprepared analogously to processes known per se of the prior art,according to the syntheses shown in the schemes below:

In scheme 1, n, R^(a), R¹, R², R³, X and Y are as defined above. R isC₁-C₄-alkyl, in particular methyl or ethyl, W is C₁-C₆-alkyl,C₁-C₆-alkoxy, in particular methoxy or ethoxy, C₁-C₆-haloalkyl,optionally substituted C₃-C₈-cycloalkyl, optionally substitutedC₅-C₈-cycloalkenyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl and U is OH,C₁-C₆-alkyl, C₁-C₆-haloalkyl, optionally substituted C₃-C₈-cycloalkyl,optionally substituted C₅-C₈-cycloalkenyl, C₂-C₆-alkenyl orC₂-C₆-alkynyl.

According to scheme 1, in a first step, a hetarylamine of the formula IIis condensed with a CH-acidic compound of the formula III. Examples ofsuitable CH-acidic compounds of the formula III are substituted(C₁-C₄)-alkyl phenylacetates and substituted benzyl (halo)alkyl ketones,benzyl cycloalkyl ketones, benzyl alkenyl ketones, benzyl cycloalkenylketones and benzyl alkynyl ketones. Examples of suitable hetarylaminesof the formula II are 2-aminopyridine-3-carboxylic esters(2-aminonicotinic esters), 3-aminopyrazine-2-carboxylic esters and4-aminopyrimidine-5-carboxylic esters.

Thus, when using 2-aminopyridine-3-carboxylic esters (2-aminonicotinicesters) are used, the compounds I.a where R¹=OH are obtained; when using3-aminopyrazine-2-carboxylic esters, the compounds I.b where R¹=OH areobtained and when using 4-aminopyrimidine-5-carboxylic esters, thecompounds I.c where R¹=OH are obtained.

The condensation is generally carried out in the presence of a Brønstedor Lewis acid as acidic catalyst or in the presence of a basic catalyst;see, for example, Organikum, 15th edition, VEB Deutscher Verlag derWissenschaften, Berlin 1976, 552ff. Examples of suitable acidiccatalysts are zinc chloride, phosphoric acid, hydrochloric acid, aceticacid and also mixtures of acetic acid and zinc chloride. Examples ofsuitable basic catalysts are inorganic and organic basic catalysts.Suitable inorganic basic catalysts are, for example, alkali metal oralkaline earth metal hydrides, preferably alkali metal hydrides, such assodium hydride or potassium hydride, and alkali metal and alkaline earthmetal hydroxides, such as sodium hydroxide or potassium hydroxide. Whensubstituted phenylacetic esters are used, the condensation canfurthermore be carried out in the presence of metallic sodium. Examplesof suitable organic basic catalysts are alkali metal or alkaline earthmetal alkoxides, such as sodium methoxide, sodium ethoxide, sodiumn-propoxide, sodium isopropoxide, sodium n-butoxide, sodiumsec-butoxide, sodium tert-butoxide, potassium methoxide, potassiumethoxide, potassium n-propoxide, potassium isopropoxide, potassiumn-butoxide, potassium sec-butoxide, potassium tert-butoxide, secondaryamines, such as ethyldiisopropylamine, and amidine bases, such as1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

The reaction can be carried out in the absence of a solvent or in asolvent. In the absence of a solvent, the CH-acidic compound III isusually employed in excess, based on the hetarylamine.

Condensation reactions of a hetarylamine of the formula II with asuitably substituted phenylacetic ester of the formula III are known inprinciple from the literature, for example from Archiv der Pharmazie,290, 1957, 136, Chem. Ber. 96, 1963, 1868, Chem. Ber. 111, 1978,2813-2824 or J. Heterocyclic Chem. 30, 909 (1963), and can be utilizedin an analogous manner for preparing the compounds according to theinvention.

In the condensation shown in scheme 1, when using phenylacetic esters ofthe formula II, compounds I are obtained in which R¹ and R² are eachhydroxyl. If ketones of the formula III are employed, compounds I areobtained where R¹=hydroxyl and R²=C₁-C₆-(halo)alkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, optionally substituted C₃-C₈-cycloalkyl or optionallysubstituted C₅-C₈-cycloalkenyl.

Such compounds I (R¹=OH) are of particular interest as intermediates forthe preparation of other compounds I. In one or more steps, the OHgroup(s) in these compounds can be converted into other functionalgroups. To this end, the OH group(s) will generally initially beconverted into halogen, in particular chlorine (see scheme 1a).

In scheme 1a, the variables n, R^(a), R³, X and Y are as defined above.This conversion succeeds, for example, by reacting I {R¹=OH, R²=OH,C₁-C₆-(halo)alkyl, optionally substituted C₃-C₈-cycloalkyl} with asuitable halogenating agent (shown in scheme 1a for a chlorinating agent[Cl]). This method is known in principle, for example, from Archiv derPharmazie, 290, 1957, p. 136 or J. Heterocyclic Chem., 30, 909 (1993).

Suitable halogenating agents are, for example, phosphorus trihalides,phosphorus oxyhalides or phosphorus pentahalides, such as phosphorustribromide, phosphorus oxytribromide, and in particular chlorinatingagents such as POCl₃, PCl₃/Cl₂ or PCl₅, and mixtures of these reagents.For the chlorination, preference is given to using a mixture ofphosphorus pentachloride and phosphorus oxychloride. The reaction can becarried out in excess halogenating agent (POCl₃) or an inert solvent,such as, for example, acetonitrile or 1,2-dichloroethane.

This reaction is usually carried out between 10 and 180° C. Forpractical reasons, the reaction temperature frequently corresponds tothe boiling point of the chlorinating agent (POCl₃) used or of thesolvent. The process is, if appropriate, carried out with addition ofN,N-dimethylformamide or nitrogen bases, such as, for example,N,N-dimethylaniline, in catalytic or stoichiometric amounts.

The monohalo compounds I obtained in this reaction, for example thechloro compound I {R¹=Cl; R²=C₁-C₆-(halo)alkyl, optionally substitutedC₃-C₈-cycloalkyl} or the dichloro compound I {R¹=R²=Cl} can then beconverted analogously to known processes from the prior art into othercompounds I.

Compounds of the formula I in which R¹ is OR⁶ are obtained from thecorresponding chloro compounds of the formula I {R¹=Cl, R²=alkyl,haloalkyl, cycloalkyl} by reaction with alkali metal hydroxides{OR⁶=OH}, alkali metal or alkaline earth metal alkoxides {OR⁶=O-alkyl,O-haloalkyl}[cf.: Heterocycles, Vol. 32, pp. 1327-1340 (1991); J.Heterocycl. Chem. Vol. 19, pp. 1565-1567 (1982); Geterotsikl. Soedin,pp. 400-402 (1991)]. The esterification of compounds where R¹=OH bymethods known per se affords compounds I in which R¹ is O—C(O)R⁹.Compounds where R¹=OH can also be converted by etherification methodsknown per se into the corresponding compounds I in which R¹ is O-alkyl,O-haloalkyl or O-alkenyl.

Compounds of the formula I in which R¹ is cyano can be obtained from thecorresponding chloro compounds of the formula I {R¹=Cl, R²=alkyl,haloalkyl, cycloalkyl} by reaction with alkali metal, alkaline earthmetal or metal cyanides, such as NaCN, KCN or Zn(CN)₂ [cf.:Heterocycles, Vol. 39, pp. 345-356 (1994); Collect. Czech. Chem. Commun.Vol. 60, pp. 1386-1389 (1995); Acta Chim. Scand., Vol. 50, pp. 58-63(1996)].

Compounds of the formula I in which R¹ is halogen and compounds of theformula I in which R¹ and R² are both halogen are therefore ofparticular interest as intermediates for preparing other compounds I. Anoverview over further such conversions is given by schemes 1b, 1c and1d.

Thus, for example, as shown in scheme 1b, the monochloro compound I{R¹=Cl, R²=C₁-C₆-(halo)alkyl, optionally substituted C₃-C₈-cycloalkyl}can be reacted with an amine HNR⁷R⁸, in which R⁷ and R⁸ are as definedabove, which gives a compound I in which R¹ is NR⁷R⁸ and R² isC₁-C₆-(halo)alkyl, optionally substituted C₃-C₈-cycloalkyl. If thedichloro compound I {R¹=R²=Cl} is reacted with an amine HNR⁷R⁸ in whichR⁷ and R⁸ are as defined above, a compound I in which R¹ is chlorine andR² is NR⁷R⁸ is obtained.

In scheme 1b, the variables n, R^(a), R³, R⁷, R⁸, X and Y are as definedabove.

The reaction of the monochloro compound I {R¹=Cl, R²=C₁-C₆-alkyl,C₁-C₆-haloalkyl or optionally substituted C₃-C₈-cycloalkyl} or thedichloro compounds I {R¹=R²=Cl} with an amine HNR⁷R⁸ is usually carriedout at from 0 to 150° C., preferably at from 10 to 120° C., in an inertsolvent, if appropriate in the presence of an auxiliary base. Thismethod is known in principle, for example from II Farmaco, 57, 2002,631, and can be applied in a manner analogous to the preparation of thecompounds according to the invention.

Suitable solvents are protic solvents, such as alcohols, for exampleethanol, and also aprotic solvents, for example aromatic hydrocarbons,halohydrocarbons and ethers, e.g. toluene, o-, m- and p-xylene, diethylether, diisopropyl ether, tert-butyl methyl ether, dioxane,tetrahydrofuran, dichloromethane, and also mixtures of the solventsmentioned above. Suitable auxiliary bases are, for example, thosementioned below: alkali metal carbonates and hydrogencarbonates, such asNaHCO₃ and Na₂CO₃, alkali metal hydrogenphosphates, such as Na₂HPO₄,alkali metal borates, such as Na₂B₄O₇, tertiary amines, such astriethylamine, ethyldiisopropylamine or diethylaniline, and pyridinecompounds. A suitable auxiliary base is also an excess of the amineHNR⁷R⁸.

Usually, the components are employed in an approximately stoichiometricratio. However, it can be advantageous to use an excess of amine HNR⁷R⁸.When using an excess of amine HNR⁷R⁸, the amine can simultaneously actas solvent. The amines HNR⁷R⁸ are commercially available or known fromthe literature, or they can be prepared by known methods.

Compounds of the formula I in which R² is O—C₁-C₄-alkylphenyl, wherephenyl is optionally mono- or polysubstituted, can also be prepared fromthe corresponding dichloro compound I {R¹=Cl, R²=Cl} by reaction with analcohol R⁶OH, as shown in scheme 1c. Such reactions are known inprinciple, for example from JACS, 69, 1947, 1204. The reaction isgenerally carried out in the presence of a base. Suitable bases arealkali metal hydrides, such as sodium hydride or potassium hydride,alkali metal or alkaline earth metal alkoxides, such as sodiumt-butoxide or potassium tert-butoxide, or tertiary amines, such astriethylamine or pyridine. Alternatively, the alcohol R⁶OH can alsoinitially be reacted with an alkali metal, preferably sodium, withformation of the corresponding alkoxide. The reaction can be carried outin excess alcohol or in an inert solvent, such as a carboxamide, forexample N,N-dimethylformamide, N,N-dimethylacetamide orN-methylpyrrolidone. The reaction is usually carried out at from 0° C.to 150° C., preferably at from 10° C. to 100° C.

In scheme 1c, n, R^(a), R³, X and Y are as defined above, and the phenylradical in R⁶ may optionally be mono- or polysubstituted by alkyl,alkoxy or halogen.

Compounds of the formula I in which R¹ is NR⁷R⁸ and R² is halogen, inparticular chlorine, can be obtained, for example, from thecorresponding halogen compounds of the formula I {R¹=halogen, R²=OR⁶,where R⁶=phenyl-C₁-C₄-alkyl). The reaction sequence is shown in scheme1d for the preparation of compounds I where R¹=NR⁷R⁸ and R²=Cl. Inscheme 1d, n, R^(a), R³, R⁷, R⁸, X and Y are as defined above, and thephenyl radical in R⁶ may optionally be mono- or polysubstituted byalkyl, alkoxy or halogen.

The reaction shown in step a) can be carried out in a known manner, forexample analogously to the method shown in scheme 1b. In the resultingcompound I {R¹=NR⁷R⁸ and R²=OR⁶, where R⁶=phenyl-C₁-C₄-alkyl}, the etherbond can be cleaved by catalytic hydrogenolysis, for example accordingto the method described in Org. Lett., 3, 2001, 4263. Suitable catalystsare, for example, noble metals or transition metals, such as palladiumor platinum. In general, the catalyst is supported, for example onactivated carbon. The hydrogenolysis is usually carried out in asolvent. Suitable solvents are, for example, alcohols, such as methanol,or cyclic ethers, such as tetrahydrofuran or dioxane. In general, thehydrogenolysis is carried out under atmospheric pressure. Thehydrogenolysis is generally carried out at temperatures between roomtemperature and the boiling point of the solvent, preferably attemperatures between room temperature and 40° C.

The compounds of the formula I obtained in this manner where R¹=NR⁷R⁸and R²=OH can then be converted into the corresponding compounds whereR¹=NR⁷R⁸ and R²=halogen, preferably chlorine. Processes for convertingalcohols into the corresponding halides are known from the prior art,for example from J. Chem. Soc. 1947, 899. Suitable halogenating agentsare, for example, the halogenating agents mentioned above (see scheme1a). The reaction can be carried out in excess halogenating agent, forexample POCl₃, or in an inert solvent, such as acetonitrile or1,2-dichloroethane.

The reaction is generally carried out between 10 and 180° C., preferablybetween room temperature and 130° C.

Compounds of the formula I in which R² is cyano can be obtained from thecorresponding chloro compounds of the formula I {R¹=NR⁷R⁸, R²=Cl} byreaction with alkali metal, alkaline earth metal or metal cyanides, suchas NaCN, KCN or Zn(CN)₂ [cf.: Heterocycles, Vol. 39, pp. 345-356 (1994);Collect. Czech. Chem. Commun. Vol. 60, pp. 1386-1389 (1995); Acta Chim.Scand., Vol. 50, pp. 58-63 (1996)].

The conversion of chloro compounds of the formula I {R¹=NR⁷R⁸, R²=Cl}into compounds of the formula I in which R² is C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, optionally substitutedC₃-C₈-cycloalkyl or optionally substituted C₅-C₈-cycloalkenyl can becarried out in a manner known per se by reacting organometalliccompounds R^(2a)-Met in which R², is C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, optionally substituted C₃-C₈-cycloalkyl oroptionally substituted C₅-C₈-cycloalkenyl and Met is lithium, magnesiumor zinc. The reaction is preferably carried out in the presence ofcatalytic or, in particular, at least equimolar amounts of transitionmetal salts and/or compounds, in particular in the presence of Cu salts,such as Cu(I) halides and especially Cu(I) iodide. In general, thereaction is carried out in an inert organic solvent, for example anether, in particular tetrahydrofuran, an aliphatic or cycloaliphatichydrocarbon, such as hexane, cyclohexane and the like, an aromatichydrocarbon, such as toluene, or in a mixture of these solvents. Therequired temperatures are in the range from −100 to +100° C. andespecially in the range from −80° C. to +40° C.

Analogously, it is possible to convert chloro compounds of the formula I{R¹=Cl, R²=NR⁷R⁸}, in which R¹ is C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl.

Compounds of the formula I in which R¹ is C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl canbe prepared, for example, by reacting the chloro compound I {R¹=Cl andR²=alkyl, cycloalkyl) in the manner described above with organometalliccompounds R^(1a), where R^(1a) is C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, optionally substituted C₃-C₈-cycloalkyl oroptionally substituted C₅-C₈-cycloalkyl and Met is lithium, magnesium orzinc.

By appropriate modification of the synthesis shown in scheme 1b, it ispossible to introduce, instead of the group NR⁷R⁸, a nitrile group, agroup OR^(6′) {R^(6′)=alkyl} or a group S—R^(6″) {R^(6″)=H or alkyl} assubstituent R¹ into compounds I where R¹=Cl and R²=alkyl, haloalkyl oroptionally substituted alkyl, using the methods mentioned here.

Some of the hetarylamines of the formula II are commercially availableor known from the literature, or they can be prepared analogously toprocesses known from the literature, for example J. Chem. Soc. 1937,367; J. Chem. Soc. 1953, 331; Bioorg. Med. Chem. 9, (2001) 2061; JACS67, 1945, 1711.

Substituted phenylacetic esters of the formula III are known from theliterature or can be prepared analogously to known processes.

The ketones of the formula III used as starting materials are usefulstarting materials for preparing the compounds I according to theinvention {R²=C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono- orpolysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which isoptionally mono- or polysubstituted by alkyl and/or halogen}.

The ketones of the formula III are novel if the radical

is a radical of the formula

in which

-   R^(a1) is fluorine, chlorine, trifluoromethyl or methyl;-   R^(a2) is hydrogen or fluorine;-   R^(a3) is hydrogen, fluorine, chlorine, cyano, C₁-C₄-alkyl,    especially methyl, C₁-C₄-alkoxy, especially methoxy, or    C₁-C₄-alkoxycarbonyl, especially methoxycarbonyl;-   R^(a4) is hydrogen, chlorine or fluorine;-   R^(a5) is hydrogen, fluorine, chlorine or C₁-C₄-alkyl, especially    methyl, or C₁-C₄-alkoxy, especially methoxy.

Accordingly, the present invention also provides ketones of the formulaIIID

in which

-   R^(a1), R^(a2), R^(a3), R^(a4) and R^(a5) are as defined above and-   W′ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl,    C₃-C₈-cycloalkyl which is optionally mono- or polysubstituted by    alkyl and/or halogen, C₅-C₈-cycloalkenyl which is optionally mono-    or polysubstituted by alkyl and/or halogen.

Preferably, W′ is C₁-C₆-alkyl, in particular methyl. Preferably, atleast one of the radicals R^(a3) or R^(a5) is different from hydrogen.Preferably, at least one and particularly preferably both radicalsR^(a2), R^(a4) are hydrogen.

In a very particularly preferred embodiment of the present invention,(R^(a))_(n) is 2-CH₃-4-Cl, 2-F-4-CH₃, 2,6-di-F-4-CH₃, 2,6-di-F-4-CN,2,6-di-F-4-COOCH₃, 2-CF₃-4-F, 2-CF₃-5-F, 2-CF₃-5-Cl, 2-F-6-CH₃,2,6-di-F-4-OCH₃, 2-CH₃-4-F, 2-F-6-OCH₃, 2-F-4-Cl, 2-Cl-4-F, 2,5-di-F,2,4,6-tri-F or 2,3,4-tri-F.

The ketones of the formula III, in particular the ketones of the formulaIIID, can be prepared, for example, according to scheme 2 by heating aphenyl-β-keto ester of the formula IV in the presence of a weak aqueousacid, for example lithium chloride.

In scheme 2, R^(a) and n have the meanings mentioned above, inparticular the meanings mentioned as being preferred, W′ is C₁-C₆-alkyl,C₁-C₆-haloalkyl, optionally substituted C₃-C₈-cycloalkyl, optionallysubstituted C₅-C₈-cycloalkenyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl. In apreferred embodiment of the present invention, the compound IV isemployed as its ethyl ester.

In general, the acid is employed in excess, based on the phenyl-β-ketoester IV. Usually, the phenyl-β-keto ester IV is heated in a solvent.Suitable solvents are dipolar aprotic solvents, such as dimethylsulfoxide. The reaction temperature is usually in the range from roomtemperature to the boiling point of the solvent, preferably in the rangefrom 60° C. to the boiling point of the solvent. The phenyl-β-ketoesters IV are either known from the literature, for example from WO99/41255, or they can be prepared analogously to processes known fromthe literature, for example analogously to Houben-Weyl, Volume VII/2a,p. 521.

The compounds I are suitable as fungicides. They are distinguished by anoutstanding effectiveness against a broad spectrum of phytopathogenicfungi, especially from the class of the Ascomycetes, Deuteromycetes,Oomycetes and Basidiomycetes. Some are systemically effective and can beused in crop protection as foliar and soil fungicides.

They are particularly important in the control of a multitude of fungion various cultivated plants, such as wheat, rye, barley, oats, rice,corn, grass, bananas, cotton, soybean, coffee, sugar cane, vines, fruitsand ornamental plants, and vegetables, such as cucumbers, beans,tomatoes, potatoes and cucurbits, and on the seeds of these plants.

They are especially suitable for controlling the following plantdiseases:

Alternaria species on fruit and vegetables,

Bipolaris and Drechslera species on cereals, rice and lawns,

-   -   Blumeria graminis (powdery mildew) on cereals,    -   Botrytis cinerea (gray mold) on strawberries, vegetables,        ornamental plants and grapevines,    -   Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,    -   Fusarium and Verticillium species on various plants,    -   Mycosphaerella species on cereals, bananas and peanuts,    -   Phytophthora infestans on potatoes and tomatoes,    -   Plasmopara viticola on grapevines,    -   Podosphaera leucotricha on apples,    -   Pseudocercosporella herpotrichoides on wheat and barley,    -   Pseudoperonospora species on hops and cucumbers,    -   Puccinia species on cereals,    -   Pyricularia oryzae on rice,    -   Rhizoctonia species on cotton, rice and lawns,    -   Rhynchosporium secalis (leaf blotch) on cereals,    -   Septoria tritici and Stagonospora nodorum on wheat,    -   Uncinula necator on grapevines,    -   Ustilago species on cereals and sugar cane, and    -   Venturia species (scab) on apples and pears.

The compounds I are also suitable for controlling harmful fungi, such asPaecilomyces variotii, in the protection of materials (e.g. wood, paper,paint dispersions, fibers or fabrics) and in the protection of storedproducts.

The compounds I are employed by treating the fungi or the plants, seeds,materials or soil to be protected from fungal attack with a fungicidallyeffective amount of the active compounds. The application can be carriedout both before and after the infection of the materials, plants orseeds by the fungi.

The fungicidal compositions generally comprise between 0.1 and 95%,preferably between 0.5 and 90%, by weight of active compound.

When employed in crop protection, the amounts applied are, depending onthe kind of effect desired, between 0.01 and 2.0 kg of active compoundper ha.

In seed treatment, amounts of active compound of 0.001 to 1 g,preferably 0.01 to 0.05 g, per kilogram of seed are generally required.

When used in the protection of materials or stored products, the amountof active compound applied depends on the kind of application area andon the desired effect. Amounts customarily applied in the protection ofmaterials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg,of active compound per cubic meter of treated material.

The compounds I can be converted into the customary formulations, forexample solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application form depends on the particular purpose; ineach case, it should ensure a fine and uniform distribution of thecompound according to the invention.

The formulations are prepared in a known way, e.g. by extending theactive compound with solvents and/or carriers, if desired usingemulsifiers and dispersants, it being possible, when water is thediluent, also to use other organic solvents as auxiliary solvents.Suitable auxiliaries for this purpose are essentially: solvents, such asaromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol),ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethylformamide) and water; carriers, such as ground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g.highly dispersed silica, silicates); emulsifiers, such as nonionic andanionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants, such aslignosulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid and dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids, andalkali metal and alkaline earth metal salts thereof, salts of sulfatedfatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or of naphthalenesulfonic acid with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, octylphenol and nonylphenol, alkylphenol polyglycolethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignosulfite waste liquors and methylcellulose.

Mineral oil fractions having medium to high boiling points, such askerosene or diesel fuel, furthermore coal tar oils, and oils ofvegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons,e.g. benzene, toluene, xylene, paraffin, tetrahydronaphthalene,alkylated naphthalenes or derivatives thereof, methanol, ethanol,propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol,cyclohexanone, chlorobenzene or isophorone, or highly polar solvents,e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone orwater, are suitable for the preparation of directly sprayable solutions,emulsions, pastes or oil dispersions.

Powders, preparations for broadcasting and dusts can be prepared bymixing or grinding the active substances together with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active compounds to solidcarriers. Solid carriers are, e.g., mineral earths, such as silica gels,silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such as, e.g.,ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, andplant products, such as cereal meal, tree bark meal, wood meal andnutshell meal, cellulose powders and other solid carriers.

The formulations generally comprise between 0.01 and 95% by weight,preferably between 0.1 and 90% by weight, of the active compound. Theactive compounds are employed therein in a purity of 90% to 100%,preferably 95% to 100% (according to the NMR spectrum).

Examples for formulations are:

-   I. 5 parts by weight of a compound according to the invention are    intimately mixed with 95 parts by weight of finely divided kaolin.    In this way, a dust comprising 5% by weight of the active compound    is obtained.-   II. 30 parts by weight of a compound according to the invention are    intimately mixed with a mixture of 92 parts by weight of pulverulent    silica gel and 8 parts by weight of liquid paraffin, which had been    sprayed onto the surface of this silica gel. In this way, an active    compound preparation with good adhesive properties (active compound    content 23% by weight) is obtained.-   III. 10 parts by weight of a compound according to the invention are    dissolved in a mixture consisting of 90 parts by weight of xylene, 6    parts by weight of the addition product of 8 to 10 mol of ethylene    oxide with 1 mol of the N-monoethanolamide of oleic acid, 2 parts by    weight of the calcium salt of dodecylbenzenesulfonic acid and 2    parts by weight of the addition product of 40 mol of ethylene oxide    with 1 mol of castor oil (active compound content 9% by weight).-   IV. 20 parts by weight of a compound according to the invention are    dissolved in a mixture consisting of 60 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight    of the addition product of 7 mol of ethylene oxide with 1 mol of    isooctylphenol and 5 parts by weight of the addition product of 40    mol of ethylene oxide with 1 mol of castor oil (active compound    content 16% by weight).-   V. 80 parts by weight of a compound according to the invention are    intimately mixed with 3 parts by weight of the sodium salt of    diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the    sodium salt of a lignosulfonic acid from a sulfite waste liquor and    7 parts by weight of pulverulent silica gel and are ground in a    hammer mill (active compound content 80% by weight).-   VI. 90 parts by weight of a compound according to the invention are    mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a    solution is obtained which is suitable for use in the form of very    small drops (active compound content 90% by weight).-   VII. 20 parts by weight of a compound according to the invention are    dissolved in a mixture consisting of 40 parts by weight of    cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight    of the addition product of 7 mol of ethylene oxide with 1 mol of    isooctylphenol and 10 parts by weight of the addition product of 40    mol of ethylene oxide with 1 mol of castor oil. By pouring the    solution into 100 000 parts by weight of water and finely dispersing    it therein, an aqueous dispersion is obtained comprising 0.02% by    weight of the active compound.-   VIII. 20 parts by weight of a compound according to the invention    are intimately mixed with 3 parts by weight of the sodium salt of    diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the    sodium salt of a lignosulfonic acid from a sulfite waste liquor and    60 parts by weight of pulverulent silica gel and are ground in a    hammer mill. A spray emulsion comprising 0.1% by weight of the    active compound is obtained by fine dispersion of the mixture in 20    000 parts by weight of water.

The active compounds can be used as such, in the form of theirformulations or of the application forms prepared therefrom, e.g. in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dusts, preparations forbroadcasting or granules, by spraying, atomizing, dusting, broadcastingor watering. The application forms depend entirely on the intended uses;they should always ensure the finest possible dispersion of the activecompounds according to the invention.

Aqueous use forms can be prepared from emulsifiable concentrates, pastesor wettable powders (spray powders, oil dispersions) by addition ofwater. To prepare emulsions, pastes or oil dispersions, the substancescan be homogenized in water, as such or dissolved in an oil or solvent,by means of wetting agents, tackifiers, dispersants or emulsifiers.However, concentrates comprising active substance, wetting agent,tackifier, dispersant or emulsifier and possibly solvent or oil can alsobe prepared and are suitable for dilution with water.

The concentrations of active compound in the ready-for-use preparationscan be varied within relatively wide ranges. In general, they arebetween 0.0001 and 10%, preferably between 0.01 and 1%.

The active compounds can also be used with good success in the ultra lowvolume (ULV) process, it being possible to apply formulations with morethan 95% by weight of active compound or even the active compoundwithout additives.

Oils of various types, herbicides, fungicides, other pesticides andbactericides can be added to the active compounds, if appropriate evennot until immediately before use (tank mix). These agents can be addedto the preparations according to the invention in a weight ratio of 1:10to 10:1.

The preparations according to the invention can, in the application formas fungicides, also be present together with other active compounds,e.g. with herbicides, insecticides, growth regulators, fungicides oralso with fertilizers. On mixing the compounds I or the preparationscomprising them in the application form as fungicides with otherfungicides, in many cases an expansion of the fungicidal spectrum ofactivity is obtained.

The following list of fungicides, with which the compounds according tothe invention can be used in conjunction, is intended to illustrate thepossible combinations but not to limit them:

-   -   acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,    -   amine derivatives, such as aldimorph, dodine, dodemorph,        fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine        or tridemorph,    -   anilinopyrimidines, such as pyrimethanil, mepanipyrim or        cyprodinil,    -   antibiotics, such as cycloheximide, griseofulvin, kasugamycin,        natamycin, polyoxin or streptomycin,    -   azoles, such as bitertanol, bromoconazole, cyproconazole,        difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole,        fluquinconazole, flusilazole, hexaconazole, imazalil,        metconazole, myclobutanil, penconazole, propiconazole,        prochloraz, prothioconazole, tebuconazole, triadimefon,        triadimenol, triflumizole or triticonazole,    -   dicarboximides, such as iprodione, myclozolin, procymidone or        vinclozolin,    -   dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam,        metiram, propineb, polycarbamate, thiram, ziram or zineb,    -   heterocyclic compounds, such as anilazine, benomyl, boscalid,        carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet,        dithianon, famoxadone, fenamidone, fenarimol, fuberidazole,        flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol,        probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen,        silthiofam, thiabendazole, thifluzamide, thiophanate-methyl,        tiadinil, tricyclazole or triforine,    -   copper fungicides, such as Bordeaux mixture, copper acetate,        copper oxychloride or basic copper sulfate,    -   nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton        or nitrophthal-isopropyl,    -   phenylpyrroles, such as fenpiclonil or fludioxonil,    -   sulfur,    -   other fungicides, such as acibenzolar-S-methyl, benthiavalicarb,        carpropamid, chlorothalonil, cyflufenamid, cymoxanil, dazomet,        diclomezine, diclocymet, diethofencarb, edifenphos, ethaboxam,        fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam,        fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene,        metrafenone, pencycuron, propamocarb, phthalide,        tolclofos-methyl, quintozene or zoxamide,    -   strobilurins, such as azoxystrobin, dimoxystrobin,        fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,        picoxystrobin, pyraclostrobin or trifloxystrobin,    -   sulfenic acid derivatives, such as captafol, captan,        dichlofluanid, folpet or tolylfluanid,    -   cinnamides and analogous compounds, such as dimethomorph,        flumetover or flumorph.

SYNTHESIS EXAMPLES

The procedures described in the following synthesis examples were usedto prepare further compounds I by appropriate modification of thestarting compounds. The compounds thus obtained are listed in thefollowing table, together with physical data.

Precursor Example 1 1-(2,4,6-Trifluorophenyl)propan-2-one

A little at a time, 42.4 g (0.103 mol) of lithium chloride were added to15 g (0.052 mol) of ethyl 3-oxo-2-(2,4,6-trifluorophenyl)butanoate in100 ml of dimethyl sulfoxide. 18 g (0.052 mol) of water were then addeddropwise, and the resulting reaction mixture was stirred at 110° C. for6.5 hours. The reaction mixture was cooled, 50 ml of water were addedand the aqueous reaction mixture was extracted repeatedly withcyclohexane. The combined organic phases were dried, the drying agentwas then filtered off and the filtrate was concentrated. The residueobtained was chromatographed on silica gel (cyclohexane/ethyl acetate99:1), which gave, after concentration, 4.5 g (46%) of the titlecompound.

In an analogous manner, it is possible to obtain the compounds IIIlisted in Table 1 below: TABLE 1 (III)

Precursor example (R^(a))_(n) Precursor example 2 2-CH₃-4-Cl Precursorexample 3 2-F-4-CH₃ Precursor example 4 2,6-di-F-4-CH₃ Precursor example5 2,6-di-F-4-CN Precursor example 6 2,6-di-4-COOCH₃ Precursor example 72-CF₃-4-F Precursor example 8 2-CF₃-5-F Precursor example 9 2-CF₃-5-ClPrecursor example 10 2-F-6-CH₃ Precursor example 11 2,6-di-F-4-OCH₃Precursor example 12 2-CH₃-4-F Precursor example 13 2-F-6-OCH₃ Precursorexample 14 2-F-4-Cl Precursor example 15 2-Cl-4-F Precursor example 162,5-di-F Precursor example 17 2,3,4-tri-F

Example 1 6-(2,4,6-Trifluorophenyl)pyrido[2,3-d]pyrimidine-5,7-diol

At room temperature, 2.44 g (0.036 mol) of sodium ethoxide were added to6.7 g (0.033 mol) of ethyl 2,4,6-trifluorophenylacetate, and the mixturewas stirred for about 5 minutes. 3 g (0.018 mol) of ethyl4-aminopyrimidine-5-carboxylate were then added, and the resultingsuspension was heated to 130° C. To improve the stirrability of thesuspension, a further 8 ml of ethyl 2,4,6-trifluorophenylacetate wereadded. The suspension was heated for 6 hours, and the ethanol formed wasdistilled off. The reaction mixture was then allowed to cool and pouredinto water.

The aqueous reaction mixture was extracted with ethyl acetate. Theorganic layer was dried, the drying agent was filtered off and thefiltrate was evaporated to dryness, which resulted in the recovery of8.6 g of ethyl 2,4,6-trifluorophenylacetate. Using acetic acid, theaqueous phase was adjusted to a pH of 5.5, which resulted in theprecipitation of a solid. The precipitated solid was filtered off anddried, which gave 1.6 g (30%) of the title compound.

Example 2 5,7-Dichloro-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine

With stirring, 7.74 g (0.037 mol) of phosphorus pentachloride were addedto 4.2 g (0.014 mol) of6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine-5,7-diol from Example 1in 40 ml of phosphorus oxychloride, and the mixture was heated withstirring at 130° C. for 8 hours. After cooling, the reaction mixture wasconcentrated and the residue was taken up in dichloromethane. 150 ml ofwater were then added cautiously, and the aqueous reaction mixture wasmade alkaline using sodium carbonate solution. The organic phase wasseparated off, the aqueous phase was extracted twice withdichloromethane and the combined organic phases were dried. Removal ofthe drying agent by filtration and concentration of the organic phasegave 4.4 g (95%) of the title compound.

Example 37-Benzyloxy-5-chloro-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine

With cooling, 10 ml of benzyl alcohol were cautiously added dropwise to0.29 g (0.0073 mol) of 60% pure sodium hydride in white mineral oil, andthe mixture was stirred at room temperature for 30 minutes. 2.4 g(0.0073 mol) of5,7-dichloro-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine fromExample 2 were then cautiously added dropwise, and the mixture wasallowed to stand at room temperature for about 100 hours. The reactionmixture was poured into water and extracted three times with ethylacetate, and the combined organic phases were dried. Removal of thedrying agent by filtration and concentration of the organic phase gave 3g (100%) of the title compound, which was slightly contaminated.

Example 45-Chloro-7-(4-methylpiperidinyl)-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine

0.1 g (0.3 mmol) of5,7-dichloro-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine fromExample 2 was dissolved in 1 ml of dichloromethane and 0.04 ml oftriethylamine. 0.03 g (3 mmol) of 4-methylpiperidine was then added, andthe mixture was stirred at room temperature for 12 hours. The reactionmixture was taken up in a little water and dichloromethane, and theorganic phase was washed with dilute aqueous hydrochloric acid. Afterdrying of the organic phase, the drying agent was filtered off and thefiltrate was evaporated to dryness, which gave 0.1 g (85%) of the titlecompound.

Example 5 2,7-Dimethyl-3-(2,4,6-trifluorophenyl)-[1,8]naphthyridin-4-ol

At 120° C., 1.3 g (0.0072 mol) of ethyl 2-amino-6-methylnicotinate and1.48 g (0.0079 mol) of 1-(2,4,6-trifluorophenyl)propan-2-one fromprecursor example 1 were, a little at a time and alternately, added to 5g of polyphosphoric acid, and, after the addition had ended, the mixturewas heated at 150° C. for another 5 hours. The reaction mixture wasallowed to cool, then about 60 ml of ice-water were added and themixture was adjusted to pH 7 using 4 N sodium hydroxide solution, whichresulted in the formation of a precipitate. The precipitate was filteredoff and dried, which gave 0.56 g of the title compound.

Example 64-Chloro-2,7-dimethyl-3-(2,4,6-trifluorophenyl)-[1,8]naphthyridine

0.147 g (0.7 mmol) of phosphorus pentachloride was added to 0.165 g(0.54 mmol) of2,7-dimethyl-3-(2,4,6-trifluorophenyl)-[1,8]naphthyridin-4-ol fromExample 5 in 1.26 ml of phosphorus oxychloride. The resulting reactionmixture was stirred at 110° C. for 3 hours and then allowed to cool,ice-water was added and the mixture was made alkaline using aqueoussodium carbonate solution. The aqueous reaction mixture was extractedfour times with dichloromethane, the combined organic phases were dried,the drying agent was filtered off and the filtrate was concentrated,which gave 0.18 g of the title compound.

Example 77-Benzyloxy-5-(4-methylpiperidinyl)-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]-pyrimidineand 5-chloro-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidin-7-ol

The reaction mixture of 0.12 g (0.3 mmol) of7-benzyloxy-5-chloro-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidinefrom Example 3, 1.5 g of 4-methylpiperidine and 0.05 g of triethylaminewas stirred at 80° C. for 3 hours. The reaction mixture was taken up inwater, and the aqueous mixture was washed three times withdichloromethane. The combined organic phases were dried, then the dryingagent was filtered off and the filtrate was concentrated. The residuewas chromatographed on silica gel using cyclohexane:ethyl acetate(95:5), which gave 0.06 g of a mixture of the title compound and5-chloro-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidin-7-ol.

Example 85-(4-Methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidin-7-ol

0.6 g (0.0013 mol) of7-benzyloxy-5-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine(80% pure) from Example 7 in 20 ml of methanol was initially charged ina laboratory hydrogenation apparatus with aerator-stirrer (2000 min⁻¹).0.03 g of Pd/C (10%) was then added, and the mixture was hydrogenateduntil the maximum amount of hydrogen had been taken up. At a temperatureof 30° C., the mixture was hydrogenated for about 90 min. The mixturewas then filtered off with suction through kieselguhr, and the residueobtained was concentrated under reduced pressure. Purification by columnchromatography gave 0.25 g (52%) of the title compound.

Example 97-Chloro-5-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidine

0.09 g (0.43 mmol) of phosphorus pentachloride was added to 0.1 g (2.67mmol) of5-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)pyrido[2,3-d]pyrimidin-7-olin 1.5 ml of phosphorus oxychloride, and the mixture was stirred at 120°C. for 5 hours. The reaction mixture was then poured into water and madealkaline using aqueous sodium carbonate solution, and the aqueousmixture was extracted with ethyl acetate. The organic phase wasseparated off and dried, the drying agent was filtered off and thefiltrate was concentrated. The residue obtained was chromatographed onsilica gel (cyclohexane/ethyl acetate), which gave, after evaporation todryness, 0.05 g (48%) of the title compound.

The compounds of the formulae I.a, I.b and I.c listed in Tables 2 to 9below were obtained in an analogous manner. TABLE 2 (I.a)

Melting point Example R³ R¹ R² [° C.] MS [M⁺]  5 CH₃ OH CH₃ 315  6 CH₃Cl CH₃ 323 10 CH₃ OH OH 287 (decomposition) 11 CH₃ Cl Cl 208 12 H OH OH345 13 H Cl Cl 115 14 CH₃ Cl C₆H₅CH₂O 15 H OH CH₃ 313 16 H Cl C₆H₅CH₂O100 17 CHCl₂ Cl Cl 141 18 CCl₃ Cl Cl  81 19 H Cl CHCl₂

TABLE 3 (I.a)

Example R³ R¹ R² Melting point [° C.] MS [M⁺] 20 CH₃ Cl CH₃

TABLE 4 (I.b)

Example R³ R¹ R² Melting point [° C.] MS [M⁺] 21 H OH OH 253 22 H ClOH >330 23 H Cl Cl

TABLE 5 (I.c)

Melting point Example R³ R¹ R² [° C.] MS [M⁺] 1 H OH OH 348(decomposition) 2 H Cl Cl 169 3 H Cl C₆H₅CH₂O 146 4 H Cl 4-CH₃- 125piperidinyl 7 H 4-CH₃- C₆H₅CH₂O 464 piperidinyl 7 H Cl OH 111 8 H 4-CH₃-OH 268 piperidinyl 9 H 4-CH₃- Cl piperidinyl 24 H Cl S-CH₃ 164 25 HS-CH₃ S-CH₃ 104

TABLE 6 (I.c)

Melting point Example R³ R¹ R² [° C.] MS [M⁺] 26 H 4-CH₃-piperidinyl OH251

TABLE 7

No. R³ R¹ R² R⁴ Physical data 27 H OH OH H 327° C. decomp. 28 H Cl Cl H200° C. 29 H Cl Cl Cl 153° C. 30 H Cl OCH₂C₆H₅ H 108° C. 31 H4-CH₃-piperidine OH H 296° C. 32 H 4-CH₃-piperidine Cl H 175° C. 33 H ClOH H 270° C. 34 H Cl CH₃ H M⁺ 291 35 H OH CH₃ H 260° C. decomp. 36 H4-CH₃-piperidine CH₃ H M⁺ 353

TABLE 8

No. R¹ R² Physical data 37 Cl 4-CH₃-piperidine M⁺ 374.8

TABLE 9

No. R³ R¹ R² R Physical data 38 H 4-CH₃-piperidine SCH₃ F 155° C. 39 HOCH₃ OCH₃ F 126° C. 40 H Cl OCH₃ F 125° C. 41 H Cl Cl H 1H NMR (CDCl₃:9.87, 9.65 2H, pyrimidine-H 42 H N(CH₃)₂ Cl F M⁺ 338.8

USE EXAMPLES

The active compounds were prepared as a stock solution with 0.25% byweight of active compound in acetone or DMSO (dimethyl sulfoxide). 1% byweight of the emulsifier Uniperol® EL (wetting agent having emulsifyingand dispersing action based on ethoxylated alkylphenols) was added tothis solution, and the solution was diluted with water to the desiredconcentration.

Activity against leaf blotch on wheat caused by Leptosphaeria nodorum,protective application.

Pots with wheat plants of the cultivar “Kanzler” were sprayed to runoffpoint with an aqueous suspension having the concentration of activecompound stated below. The next day, the pots were inoculated with anaqueous spore suspension of Leptosphaeria nodorum. The plants were thenplaced in a chamber at 20° C. and maximum atmospheric humidity. After 8days, the leaf blotch on the untreated but infected control plants haddeveloped to such an extent that the degree of infection could bedetermined visually in %. Compound Leaf infection [%] at 250 ppm

3

10

3 untreated 80

1. A bicyclic compound of the formula I

in which X, Y independently of one another are N or C—R⁴; n is 1, 2, 3,4 or 5; R^(a) is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy orC(O)R⁵; R¹ is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono-or polysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which isoptionally mono- or polysubstituted by alkyl and/or halogen, OR⁶, SR⁶ orNR⁷R⁸; R² is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono-or polysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which isoptionally mono- or polysubstituted by alkyl and/or halogen, OR⁶, SR⁶ orNR⁷R⁸; R³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl or C₃-C₆-cycloalkylwhich is optionally mono- or polysubstituted by alkyl and/or halogen; R⁴is hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl or C₃-C₆-cycloalkylwhich is optionally mono- or polysubstituted by alkyl and/or halogen; R⁵is hydrogen, OH, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl,C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₁-C₆-alkylamino ordi-C₁-C₆-alkylamino, piperidin-1-yl, pyrrolidin-1-yl or morpholin-4-yl;R⁶ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, phenyl-C₁-C₄-alkyl wherephenyl may be mono- or polysubstituted by halogen, alkyl or alkoxy,C₂-C₆-alkenyl or COR⁹; R⁷, R⁸ independently of one another are hydrogen,C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₄-C₁₀-alkadienyl, C₂-C₁₀-alkynyl,C₃-C₈-cycloalkyl, C₅-C₈-cycloalkenyl, C₅-C₁₀-bicycloalkyl, phenyl,phenyl-C₁-C₄-alkyl, naphthyl, a 5- or 6-membered saturated or partiallyunsaturated heterocycle which may have 1, 2 or 3 heteroatoms selectedfrom the group consisting of N, O and S as ring members, or a 5- or6-membered aromatic heterocycle which may have 1, 2 or 3 heteroatomsselected from the group consisting of N, O and S as ring members, wherethe radicals mentioned as R⁷, R⁸ may be partially or fully halogenatedand/or may have 1, 2 or 3 radicals R^(b), where R^(b) is selected fromthe group consisting of cyano, nitro, OH, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₂-C₆-alkenyl,C₂-C₆-alkenyloxy, C₂-C₆-alkynyl, C₂-C₆-alkynyloxy, C₁-C₆-alkylamino,di-C₁-C₆-alkylamino, piperidin-1-yl, pyrrolidin-1-yl or morpholin-4-yl;R⁷ and R⁸ together with the nitrogen atom to which they are attached mayalso form a 5-, 6- or 7-membered saturated or unsaturated heterocyclewhich may have 1, 2, 3 or 4 further heteroatoms selected from the groupconsisting of O, S, N and NR¹⁰ as ring members and may be partially orfully halogenated and which may have 1, 2 or 3 radicals R^(b); and R⁹,R¹⁰ independently of one another are hydrogen or C₁-C₆-alkyl; or anagriculturally acceptable salt of a compound I, except for the compoundsof the formula I in which R¹ is OH, if Y and X are simultaneously eachC—R⁴; and also except for2,4-dichloro-3-(o-methoxyphenyl)-1,8-naphthyridine.
 2. The compoundaccording to claim 1 of the formula I in which Y and X are each C—R⁴. 3.The compound according to claim 1 of the formula I in which Y is N and Xis C—R⁴.
 4. The compound according to claim 1 of the formula I in whichY is C—R⁴ and X is N.
 5. The compound according to any of the precedingclaims of the formula I in which R⁴ is hydrogen, C₁-C₆-alkyl orC₁-C₆-haloalkyl.
 6. The compound according to claim 1 of the formula Iin which n is 2, 3, 4 or
 5. 7. The compound according to claim 1 of theformula I in which the group

where R^(a1) is fluorine, chlorine, trifluoromethyl or methyl; R^(a2) ishydrogen or fluorine; R^(a3) is hydrogen, fluorine, chlorine, cyano,C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl; R^(a4) is hydrogen,chlorine or fluorine; R^(a5) is hydrogen, fluorine, chlorine,C₁-C₄-alkyl or C₁-C₄-alkoxy.
 8. The compound according to claim 1 of theformula I in which R¹ is a group NR⁷R⁸ in which at least one of theradicals R⁷, R⁸ is different from hydrogen.
 9. The compound according toclaim 8 of the formula I in which R⁷ is C₁-C₆-alkyl, C₃-C₈-cycloalkylwhich is optionally mono- or polysubstituted by alkyl and/or halogen,C₁-C₆-haloalkyl, phenyl-C₁-C₄-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl; R⁸is hydrogen, C₁-C₆-alkyl or C₂-C₆-alkenyl; or R⁷, R⁸ together with thenitrogen atom to which they are attached are a saturated or partiallyunsaturated 5-, 6- or 7-membered nitrogen heterocycle which may have 1further heteroatom selected from the group consisting of O, S and NR¹⁰as ring member and which may have 1 or 2 substituents selected from thegroup consisting of C₁-C₆-alkyl, C₁-C₆-haloalkyl, halogen and hydroxyl,where R¹⁰ is as defined in claim
 1. 10. The compound according to claim1 of the formula I in which R¹ is hydroxyl and one of the radicals Y orX is N.
 11. The compound according to claim 1 of the formula I in whichR¹ is halogen.
 12. The compound according to claim 1 in which R² ishydroxyl, Y is C—R⁴ and X is C—R⁴ or N.
 13. The compound according toclaim 1 in which R² is halogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl.
 14. Theuse of a compound of the formula I

in which X, Y independently of one another are N or C—R⁴; n is 1, 2, 3,4 or 5; R^(a) is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy orC(O)R⁵; R¹ is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono-or polysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which isoptionally mono- or polysubstituted by alkyl and/or halogen, OR⁶, SR⁶ orNR⁷R⁸; R² is halogen, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono-or polysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which isoptionally mono- or polysubstituted by alkyl and/or halogen, OR⁶, SR⁶ orNR⁷R⁸; R³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl or C₃-C₆-cycloalkylwhich is optionally mono- or polysubstituted by alkyl and/or halogen; R⁴is hydrogen, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl or C₃-C₆-cycloalkylwhich is optionally mono- or polysubstituted by alkyl and/or halogen; R⁵is hydrogen, OH, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl,C₁-C₆-haloalkoxy, C₂-C₆-alkenyl, C₁-C₆-alkylamino ordi-C₁-C₆-alkylamino, piperidin-1-yl, pyrrolidin-1-yl or morpholin-4-yl;R⁶ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, phenyl-C₁-C₄-alkyl wherephenyl may be mono- or polysubstituted by halogen, alkyl or alkoxy,C₂-C₆-alkenyl or COR⁹; R⁷, R⁸ independently of one another are hydrogen,C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₄-C₁₀-alkadienyl, C₂-C₁₀-alkynyl,C₃-C₈-cycloalkyl, C₅-C₈-cycloalkenyl, C₅-C₁₀-bicycloalkyl, phenyl,phenyl-C₁-C₄-alkyl, naphthyl, a 5- or 6-membered saturated or partiallyunsaturated heterocycle which may have 1, 2 or 3 heteroatoms selectedfrom the group consisting of N, O and S as ring members, or a 5- or6-membered aromatic heterocycle which may have 1, 2 or 3 heteroatomsselected from the group consisting of N, O and S as ring members, wherethe radicals mentioned as R⁷, R⁸ may be partially or fully halogenatedand/or may have 1, 2 or 3 radicals R^(b), where R^(b) is selected fromthe group consisting of cyano, nitro, OH, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₂-C₆-alkenyl,C₂-C₆-alkenyloxy, C₂-C₆-alkynyl, C₂-C₆-alkynyloxy, C₁-C₆-alkylamino,di-C₁-C₆-alkylamino, piperidin-1-yl, pyrrolidin-1-yl or morpholin-4-yl;R⁷ and R⁸ together with the nitrogen atom to which they are attached mayalso form a 5-, 6- or 7-membered saturated or unsaturated heterocyclewhich may have 1, 2, 3 or 4 further heteroatoms selected from the groupconsisting of O, S, N and NR¹⁰ as ring members, and may be partially orfully halogenated and which may have 1, 2 or 3 radicals R^(b); and R⁹,R¹⁰ independently of one another are hydrogen or C₁-C₆-alkyl; or anagriculturally acceptable salt thereof for controlling phytopathogenicfungi.
 15. A method for controlling phytopathogenic fungi, whichcomprises treating the fungi or the materials, plants, the soil or seedto be protected against fungal attack with an effective amount of acompound of the formula I according to claim 14 and/or with anagriculturally acceptable salt of I.
 16. A composition for controllingphytopathogenic fungi, comprising at least one compound of the formula Iaccording to claim 14 and/or an agriculturally acceptable salt of I andat least one liquid or solid carrier.
 17. A ketone of the formula IIID

in which W′ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl,C₂-C₆-alkynyl, C₃-C₈-cycloalkyl which is optionally mono- orpolysubstituted by alkyl and/or halogen, C₅-C₈-cycloalkenyl which isoptionally mono- or polysubstituted by alkyl and/or halogen; R^(a1) isfluorine, chlorine, trifluoromethyl or methyl; R^(a2) is hydrogen orfluorine; R^(a3) is hydrogen, fluorine, chlorine, cyano, C₁-C₄-alkyl,C₁-C₄-alkoxy or C₁-C₄-alkoxycarbonyl; R^(a4) is hydrogen, chlorine, orfluorine; R^(a5) is hydrogen, fluorine, chlorine, C₁-C₄-alkyl orC₁-C₄-alkoxy.